CN1039073A - The technology of preparation porous metal - Google Patents

The technology of preparation porous metal Download PDF

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Publication number
CN1039073A
CN1039073A CN88106090A CN88106090A CN1039073A CN 1039073 A CN1039073 A CN 1039073A CN 88106090 A CN88106090 A CN 88106090A CN 88106090 A CN88106090 A CN 88106090A CN 1039073 A CN1039073 A CN 1039073A
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metal
technology
electrode
support material
deposition
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蒋振宗
陈衍珍
蒋三平
尤金跨
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City University Of Northampton Square
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8853—Electrodeposition
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/623—Porosity of the layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0442—Anodisation, Oxidation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0454—Electrochemical coating; Electrochemical impregnation from melts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H01M4/28—Precipitating active material on the carrier
    • H01M4/29—Precipitating active material on the carrier by electrochemical methods
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0492—Chemical attack of the support material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Electrochemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

But in the technology of the metal porous layer of a kind of preparation electrolytic deposition, a support material is immersed in the electrolytic medium that contains this metal ion species, and make this metal when having a kind of oxidizing substance to exist electrolytic deposition on this support material.This oxidizing substance and this metal reaction and form a kind of product that under mode of deposition, can be reduced.In a type of this technology,, a kind of metal is deposited on the support material from the aqueous electrolyte liquid that contains this metal ion by oxygen being introduced in the medium to pass near the support material.
Present method can prepare the porous metal of high porosity, and resulting porous metal are deposited usefulness as catalytic material or electrode materials.

Description

The technology of preparation porous metal
The present invention relates to a kind of processing method for preparing porous metal, and have the goods of porous metal.The invention still further relates to a kind of method that forms porous metal oxide.
Porous metal have purposes widely, and for example: be used for battery pole plates, support of the catalyst, catalysis electrode is in strainer and the cat cracker.In these were used, with non-porous metallographic phase ratio, the porous metal with bigger surface-area had higher performance.
Previously, porous metal prepare by powder metallurgy technology.Thin metal-powder passes through pressed compact, high temperature sintering in reducing atmosphere.Be the number in the hole behind the raising sintering, pore former, for example volatile salt adds in the powder before pressed compact.Yet, in sintering process, because particle growth taken place, so the average particle size particle size of the porous metal by the sintering process preparation generally also is in the identical order of magnitude greater than the size in 5 these holes of μ.
Porous electrode is to be coated on the wire netting by oxide compound or oxyhydroxide with metal always, carries out electrochemical reduction with that in the original place and makes.The particle size of the porous metal of Xing Chenging may be in the scope more than 3 μ like this.For obtaining gratifying electroconductibility, often need the inactive conductive powder of fusion, as graphite in electrode.
In the time will being used for battery by the porous metal article of method for preparing, actual obtainable energy density be lower than theoretical value significantly.
Electrodip process is that the preparation porosity known of people is very low, or the method for the very little metal level of saying so.Make the atoms metal deposition to form closely orderly atomic shell.In the application of galvanic deposit, as in electroplating, people wish to reduce to hinder the influence that atomic shell forms in order very much as far as possible so that the porosity of the metal level that is produced minimum be understandable.
But the invention provides a kind of method that is created in the metal porous layer of the electrolytic deposition on the support material, it comprises: support material is immersed in the electrolytic medium contain this metal ion species near And a kind of and this metal reaction in the medium and when generating a kind of oxidizing substance of the product that under mode of deposition, can the be reduced support material of being provided in is arranged, with this metal deposition on support material.
Method of the present invention can prepare the metal of high hole, and Zhi Bei metal may have such as less than 3 μ therefrom, and especially less than the average particle size particle size of 1 μ, these particles are distinguished by the hole of same size as a result.
Owing to the higher porosity of the porous metallic layers for preparing by the present invention, compare with the product of prior art, having much bigger metal surface area can utilize.For example, when this metal was used in the battery electrode, the performance of this battery was compared with battery of the prior art, and tangible improvement has been arranged.Particularly big surface-area means that this electrode has high maximum current density, thereby can obtain high momentary power density.And then when this metal was used as catalyzer, high porosity had improved their catalytic performance.
Term as used herein " oxidizing substance " is to use on a kind of generalized meaning of material, and this material has improved the oxidation state of the metal of reaction with it.
Can be sure of that in technology of the present invention, oxidizing substance and sedimentary metal react and formed a kind of metallic compound, this compound then is reduced into this metal.The temporary transient existence of this metallic compound has prevented to form the metal level of densification in long-pending depositing, thereby can make the generation of porous product.
This oxidizing substance can be provided expediently, or produces continuously in the process of metal refining.
Oxidizing substance is that a kind of oxidizing substance that contains aerobic is useful.Here employed " containing oxygen " refers to and contains one or more Sauerstoffatom ， And and comprise molecular oxygen.
This contains the oxygen oxidizing substance, such as oxygen, or a kind of oxidizing substance that under mode of deposition, results from oxygen.Thereby oxidizing substance can be, maybe can result to be imported in the electrolytic medium to make it to pass the gaseous oxygen of upholder near zone.Under mode of deposition, result from containing the oxygen oxidizing substance and can being of oxygen, such as hydrogen peroxide, ozone, oxyhalogen negatively charged ion, especially hypochlorous acid negatively charged ion.
Other oxidizing substance that can be used in this comprises, such as following substances, or results from the oxidizing substance of those materials under mode of deposition: hydrogen sulfide, halogen, especially chlorine.
At least it is favourable using two kinds of oxidizing substances, is that oxygen containing oxidizing substance is preferable and have a kind of oxidizing substance at least.As mentioned above, require at least a oxidizing substance and metal reaction with produce a kind of under mode of deposition reducible product.Certainly, will be understood that, in some cases, a kind ofly can not play the effect of oxidizing substance, or produce the material of the oxidizing substance that can meet the demands in some occasion, if condition is adjusted with appropriate means, then can play this effect.Such as, although as another kind of oxidizing substance, particularly oxygen or when resulting from oxidizing substance under the mode of deposition and existing, may be with chlorion as oxidizing substance or its source, but under the condition that lacks more so other oxidizing substances, chlorion will be not according to desired mode and metal reaction.
Therefore, in preferred mode according to technology of the present invention, a kind of oxygen containing oxidizing substance, for example oxygen or the oxygen carrier that results from oxygen under mode of deposition are supplied with second oxidizing substance.This second type oxide matter can be, but need not a kind of oxygen containing oxidizing substance.Preferably, this second oxidizing substance can be, or results from halide ions, especially chloride ion or oxyhalide ion, particularly hypochlorous acid negatively charged ion.The existence of this second kind of oxidizing substance can make the porosity of porous metal be improved under many circumstances.
In pattern according to a particularly important of technology of the present invention, porous metal result from the support material, used technology comprises the support material immersion is contained in the electrolytic medium of this metal ion species, then, having mode to import under the situation of gaseous oxygen to pass through near the support material surface, with this metal deposition on support material.It is desirable containing halide ions or gaseous halogen in the electrolytic medium.Gaseous halogen can maybe blast this gas medium and they are provided by by row's condition halogen gas being overflowed on opposite electrode in ionogen, and oxygen and chlorine are introduced in the medium near the mode of introducing respectively the support material in deposition process.Under latter event, certainly can understand, leave the blast of mixture of the oxygen/halogen gas of medium for control, require to take to give anti-measure.
Employing is according to oxidizing substance of the present invention, for being that the porous metal of the mixture that constitutes of thin and thick particle provide possibility basically on the thin and thick grid close with particle size.This net in thickness hole is arranged is useful especially, in the air electrode in being widely used for metal one gas battery and fuel cell, can produce chargeable electrode.Under the situation that has oxygen to overflow, gross porosity will be drained, and the oxygen that results from the pore is overflowed effectively.Under the situation of hydrogen reduction, provide enough big air pressure in a side of the supply gas of electrode, so that the gross porosity of electrode exposes.The air pressure that only applies is not high enough to discharge the electrolytic solution in the pore, and effectively oxygen reduction reaction just can produce.
In the previous porous electrode that proposes, only be to work in the external region of electrode because when gas when electrode interior is overflowed, the electrolytic solution in the hole is discharged by bubble.Be to avoid this problem
Figure 881060909_IMG2
In the examination, used adherent polytetrafluoroethylstephanoporate stephanoporate electrode previously, in order that gas is overflowed by means of exsiccant tetrafluoroethylene duct, so that utilize resulting eelctro-catalyst surface biglyyer.Yet the existence of non-conductive particle has caused the raising of electrode resistance.In the porous metal by the inventive method preparation, the effect of gross porosity is similar to the tetrafluoroethylene duct, but electrode has all had the electroconductibility of having improved, and this is requiring high electric current (as:＞0.1 apc 2) electrochemical applications in be important.With regard to the performance of the made electrode of the porous metal of producing by method of the present invention, be the performance that is comparable to adherent poly-fluorine tetrem alkene electrode, and for the gas evolution reaction, measured ohm voltage drop has then obviously reduced.
The character that it is believed that thin and thick particulate blended structure can influence the variable of porosity and change by regulating one or more tools letter.The factor that those tool letters can influence porosity comprises the characteristic of first oxidizing substance, the existence of second oxidizing substance, if reach when having it to exist, its characteristic, the atmosphere pressures of electrolytic solution top, the pressure of the sort of gas when a kind of delivery rate of or each oxidizing substance, the concentration of electrolytic medium and temperature, oxidizing substance or its source are gas.A kind of delivery rate of oxidizing substance can be by changing, and such as changing the speed of introducing or producing oxidizing substance, or changes the slewing rate of rotating support material and change.
For example, for cobalt, produce the porous cobalt by method of the present invention from cobalt chloride solution, when producing oxygen is fed solution nearby to pass in support material, prepared porous cobalt is than having much higher porosity with similar method prepared cobalt from cobaltous acetate or cobalt sulfate solution.Yet the air with identical flow velocity replaces oxygen (air contains 20% oxygen approximately), and porosity reduces significantly.
In by the solution of ferrous chloride that is connected with oxygen, prepare in the situation of iron, find that porosity is in 3%(weight)-15%(weight) the strength of solution scope in, rising And finds that best slewing rate is 300 rev/mins with the rising of this concentration, and the porosity of the iron that is obtained under higher or lower rotating speed is lower than the porosity of the iron that is obtained under 300 rev/mins rotating speed.
Electrolytic medium can contain the ion of two or more metals, and the porous metal of making so then contain at least two kinds of metals.And can contain two or more metal ions in the electrolytic medium, wherein a kind of with a kind of product of oxidizing substance reaction generation, this product does not reduce under mode of deposition.Thereby the present invention makes and prepares a kind of porous material that contains the oxide compound of first metal and second metal and become possibility.
It is useful rotating support material in metal deposition process.In a kind of optional suitable technology, available pump makes circulation of elecrolyte, gaseous oxygen is being introduced under the occasion of this medium, and the electrolyte flow direction is relative with the flow direction of oxygen.This has increased the residence time of bubble on electrode surface, and the metal of higher deposition is plated on the support material.And then replenish in deposition process under the occasion of electrolytic solution, and under the sizable occasion of the volume of electrolytic medium, a kind of circulation of elecrolyte technology makes and keeps the composition of a metastable electrolytic solution to become possibility.Opposite electrode is that same metal is useful with the metal that is deposited.This also helps to keep the metastable concentration of this metal ion in the medium.
In general, support material is more desirable for thin stratiform, and support material can be, such as nickel screen.Other available support material comprises, such as titanium foil.In deposition process, the composition of electrolytic medium can be by adding one or more materials, as by adding solvent, a kind of salt of a kind of salt of this metal or a kind of second metal is in medium and change the zone that the porous metallic layers of making so then just is made up of many differences.
But the metal of any electrochemical deposition all can be used in the technology of the present invention, and this comprises such as the lead that is widely used as electrode materials in lead-acid battery.This metal can be selected from transition metal, and they be cobalt, iron, nickel and cadmium are useful.Other suitable transition metal comprises as zinc, silver, manganese and precious metal, as Pt, Pd, Ir.Porous transition metal goods by the present invention's preparation have superior performance in as the application in gas battery, fuel cell and the catalytic material.
As in agglutinating tetrafluoroethylene cobalt oxide/graphite air electrode, this cobalt oxide/graphite catalyst has very high activity for oxygen reduction in alkaline medium.Yet the oxide compound of cobalt is dissolved in basic solution ， And and hardly in application, under the occasion that continuous replacing alkaline electrolyte is arranged, for example in aluminium-air cell, or in chlor-alkali factory, the oxide compound of this cobalt is leached gradually, has reduced the activity of electrode therefrom.Deposition porous cobalt can make electrode regenerate in the original place on electrode according to the present invention, and electrode performance remained on the gratifying degree in long period as a result.Thereby the present invention makes cobalt/graphite air electrode replace cathode for hydrogen evolution, reduce groove and press the most nearly 0.8V as the oxygen reduction cathode in the chlor-alkali electrolysis cell, and that is to say cuts down the consumption of energy becomes possibility near 25%.
A kind of cobalt electrode also can be for example as the anode in the Ni-Co battery.
A kind of ferroelectric utmost point can be used as the anode in the Ni-Fe battery.By the prepared a kind of Fe electrode of method of the present invention, compare with the porous iron electrode of making by sintering, have much higher significantly maximum current density, thereby also have high power density.
The NiOOH electrode is used as negative electrode in the alkaline charging store battery, have weather resistance, reliability and can bear the ability of thousands of charge and discharge cycles mainly due to it.Yet, the Di ， And that the electroconductibility of NiOOH is relative and for example NiOOH to be deposited on the electroconductibility of the online electrode of Ni very poor.NiOOH often is impregnated in the sintered compact of nickel porous to obtain electroconductibility preferably.The NiOOH material of being made by the nickel porous of making by method of the present invention has that splendid electroconductibility ， And makes the NiOOH material, and a kind of application that has improved is achieved.Thereby by using the electroconductibility that method of the present invention makes the electrode that contains the NiOOH material on nickel screen, particularly its energy density and power density have been improved significantly.
Porous cadmium anode is used in the Ni-Cd battery.In the electroconductibility of the material that has improved by the prepared porous cadmium of technology of the present invention obtainable and the performance that utilization efficiency of material has been improved battery.
Electrolytic medium can be a kind of aqueous electrolytic medium.In a desirable technology, this medium is a kind ofly to contain the transition metal ion water-bearing media, and deposition current is no more than 300 milliamperes/centimetre, especially is not more than 100 milliamperes/centimetre 2
In pressing another kind of technology of the present invention, this electrolytic medium is a kind of fused salt, and this metal is a kind of refractory metal or rare earth metal, as La, Mb, W, Mo.
In foundation another technology of the present invention, this electrolytic medium is a kind of organic electrolyte, and this metal is a basic metal.Porous basic metal product is used in the organic electrolyte cell as the porous lithium product, and this needs high momentary power density.Reached the battery that surpasses prior art by the present invention obtainable high porosity, the momentary current density that has improved.
Thereby, technology of the present invention can be used for as, the preparation electrode.Advantageously after making electrode, make prepared electrode carry out the constant voltage circulation generating metal level on the support material, it has the effect of obtainable raising anode peak current when using this electrode.
Method of the present invention can also be used to electrode is regenerated in position, so just prolonged its operation life.Like this, the present invention provides a kind of electrode regenerated method in battery that makes again further, and it comprises with above-mentioned of the present invention any method form one deck porous metallic layers on electrode.In some cases, the electrolytic solution that need not to change in the battery just can make electrode regeneration.For example, in the electrolytic solution of battery, contain under the occasion that is deposited on the metal ion on the electrode, oxygen can be blasted battery electrolyte Zhong ， And can introduce as the halogenide of metal with a spot of as second oxidizing substance and/or produce the active substance in the suitable source of second oxidizing substance.And under the other situation, battery electrolyte can be changed with the ionic electrolytic solution that contains the metal that is deposited on the electrode.
Like this, the present invention can make electrode, regenerates on primary electrode as the electrode of fuel cell and air-metal battery.So far, people still are unrealized air electrode are regenerated in situ.
The present invention also provides the another kind of technology that generates metal oxide on support material, it comprises: generate porous metallic layers with above-mentioned of the present invention any method on support material, and then the generation of this porous metallic layers makes this metal level carry out anodic oxidation to form the oxide compound of this metal.This perforated metal can comprise two or more metals, and metal is allowed a choice in anodic oxidation, and the first all basically metals is oxidized, and the second all basically metals still remains on elementary state.The mixture of a kind of like this oxide compound and metal is particularly useful as catalytic material.And porous layer can contain two or more oxidized metals with formation blended oxide compound when cathode oxidation.Selecting metal in anodic oxidation like this, is useful so that these metals change into stupalith in anode oxidation process.This stupalith can be, as perovskite oxide, as the lanthanum barium-copper oxide.Perovskite oxide has caused people's attention as superconductor.Support material can be a copper.
The present invention further provides a kind of on tubing, for example form the technology of successive cramic coat on the copper pipe, this comprises: tubing is inserted in the electrolytic medium, therein, on tubing, generate porous metal according to above-mentioned of the present invention any method, after this, this tubing is put into make porous metal by anodizing to generate the zone of stupalith.So, the present invention can be covered with the tubing of ceramic layer at an easy rate with the successive explained hereafter.Such as can successive perovskite oxide, the especially copper pipe of lanthanum barium-copper oxide coating being arranged according to the present invention's preparation.In use, liquid nitrogen or other suitable cryogen can be fed in this copper pipe, under superconducting temperature, to keep this oxide material.
The present invention also provides porous metal and a kind of goods with average particle size particle size less than the porous metal part of 3 μs of a kind of average particle size particle size less than 3 μ.Thin and the thick particulate mixture that these porous metal partly are included in 0.05 μ to 1 μ scope is desirable.This product is favourable as pole plate, strainer, support of the catalyst or the catalysis electrode of battery.
The present invention will only be described in the mode of embodiment, referring to accompanying drawing, wherein:
Fig. 1 shows a kind of electrolytic cell device that is suitable for preparing according to porous metal of the present invention with the form of partial cross section and partial schematic diagram.
Fig. 2 illustrates another kind of alternative electrolytic cell device that is suitable for preparing according to porous metal of the present invention with the form of partial cross section and partial schematic diagram.
Fig. 3 shows a kind of cyclic electrolysis liquid system that is suitable for preparing by the present invention porous metal.
Fig. 4 shows the device that is similar to Fig. 3, and difference is the layout difference of support material.
The porous iron anodic volt-ampere curve of Fig. 5 for preparing according to the present invention is respectively the NiCl that adds or do not add as additive in plating bath 2Two kinds of situations.
Fig. 6 shows the volt-ampere curve by the porous iron electrode of the present invention's preparation.
Fig. 7 shows the porous cobalt electrode that is equipped with by the present invention and for relatively when having oxygen to exist, when lacking oxygen and the comparison between the anode performance of the porous cobalt electrode for preparing.
Fig. 8 shows the comparison of the cobalt electrode with higher deposition, and first kind of electrode is by prepared of the present invention, and second kind of electrode prepares with sintering method.
The constant voltage that shows Fig. 9 circulates to the influence of the porous cobalt electrode anode peak current for preparing by the present invention.
Figure 10 shows the charge and discharge volt-ampere curve by the porous cobalt electrode stable state of the present invention's preparation.
Figure 11 shows the porous nickel electrode cathodic polarization curve by the present invention's preparation.
Shown in Figure 12 is the porous cadmium electrode anodic polarization curves for preparing by the present invention.
Shown in Figure 13 is voltage one time curve that discharges under differing temps by the porous iron electrode that the present invention prepares.
Shown in Figure 14 is that the sintered iron electrode is voltage one time curve that compares with Figure 13.
Shown in Figure 15 is the porous cobalt electrode obtainable current density under different depositions for preparing by the present invention, the adherent tetrafluoroethylene after compensating with the ohm voltage drop of must hanging oneself and the porous NiCO of unbonded tetrafluoroethylene 2O 4The comparison of this value of electrode.
Shown in Figure 16 is by the performance of the cobalt electrode of the present invention's preparation and the performance of polytetrafluoroethylene electrode, and the two does not all carry out the ohm voltage drop compensation.
The preparation base material
Be used as support material with 60 purpose nickel screens.The nickel wire point is welded in this substrate as current feed, and And protects with canned Lacomit, F65441 varnish.At first this base material is dipped in the basic solution that is placed on the dilution in the sonication chamber, washes distilled removing in the ionic water then.That this this substrate of square centimeter can be garden shape or quadrate.
The preparation electrode
Any electrochemical cell that employing is shown among Fig. 1-3 prepares porous metallic layers on support material.In each situation, support material 1 is hung in the electrolytic medium 2 that is contained in the container 3.Oxygen is imported in this medium by the sintered glass plug in the support material near zone 4.Support material 1 and counter electrode 5 are electrically connected in known manner.These electrodes separate with level or vertical spaced relationship is arranged.Vertically the laying of working electrode (that is to say, when be that level is when separating between electrode) has the level of advantage (Fig. 3) electrode that makes electrolyzer more compact to lay (Fig. 4) then to make oxygen bubbles that the longer residence time is arranged on electrode surface.4 square centimeters platinum foil be used as comparative electrode and suitable saturated calomel electrode 6 as reference electrode.Working electrode (support material 1) all is rotating in each case.In deposition process, constant temperature ， And under a stable temperature imposes the constant electroplating current to plating tank with plating tank.
Fig. 3 and Fig. 4 illustrate a kind of electrolytic solution can pass through pump 7 round-robin electrolyzers.The direction of electrolyte flow is opposite with the direction of flow of oxygen.
For comparison purposes, have the metal-powder that is impregnated in the volatile salt that improves porosity by sintering in hydrogen and prepare electrode.
Embodiment 1
(a) CoCl with 70 milliliters, 10%(weight) 2Aqueous solution places the electrolyzer as Fig. 1 or type shown in Figure 2.Electrolyzer constant temperature is in 25 ℃.Electrolyzer is imposed 40 milliamperes/centimetre of constant 2Electroplating current 30 minutes.Oxygen is fed this electrolyzer by the sintered glass plug, and flow rate control is at 40 centimetres 3/ minute.This support material with 300 moving/minute speed rotate.
The porous cobalt layer color of making like this is furvous, and under similarity condition, but sedimentary cobalt is that bright De And has reflectivity when not blasting oxygen.
(b) Fecl with 70 milliliters, 10%(weight) 2Aqueous solution places a kind of electrolyzer of Fig. 1 or type shown in Figure 2.This electrolyzer constant temperature feeds 60 milliamperes/centimetre of constant in 25 ℃ And to this electrolyzer 2Electroplating current 40 minutes.Oxygen gas flow rate is controlled at 40 centimetres 3/ minute.Support material is rotated with 300 rev/mins speed.
(c) NiCl with 70 milliliters, 1%(weight) 2Aqueous solution places the electrolyzer of any class of Fig. 1-shown in Figure 3.This electrolyzer constant temperature is in 25 ℃.Feed constant, 10 milliamperes/centimetre to this electrolyzer 2Electroplating current 60 minutes.Oxygen gas flow rate is controlled at 50 centimetres 3/ minute.Working electrode is an immobilized.
(d) CdCl with 70 milliliters, 60%(weight) 2Aqueous solution is put in the arbitrary class electrolyzer shown in Fig. 1-3.This electrolyzer constant temperature feeds 6 milliamperes/centimetre of constant in 25 ℃ And to this electrolyzer 2Electric current 2 hours.Oxygen is with 10 centimetres 3/ minute flow velocity import this electrolyzer.Working electrode is an immobilized.
Embodiment 2
(a) will be to when preparation cobalt and the cadmium electrode, make solution and the influence of the anode peak current of the electrode that obtains with different electrolysis, illustrate with the result who is summarized in table 1.The condition of this metal electrode of preparation is respectively as in embodiment 1(a from metal chloride solutions) and (d) in defined.For from the acetate solution of the vitriol of metal and metal, preparing electrode, replace the chloride soln of metal respectively with the acetate solution of the sulfate liquor of metal and metal, and their concentration is identical with the concentration of metal chloride solutions.At 7 moles, measure anode peak current in 25 ℃ the KOH aqueous solution, sweep velocity is 10 millivolts/second.
As shown in table 1, by the performance that the anode peak current of measuring the electrode make from metal chloride solutions obtains, all be better than being obtained from the performance of the electrode of metal sulfate and metal acetate solution in each case.
Table 1
Metal (M) Sun level peak point current (Iap) milliampere/centimetre 2
MCl 2 MAC 2 MSO 4
Co 620 30 50
Cd 220 196 56
(b) as at embodiment 1(c) described in, from nickel chloride solution (NiCl 3) in the Performance of nickel electrode that makes be better than using the same method, but replace NiCl with nickelous acetate solution 2The performance of the prepared electrode of solution.With compare with the prepared electrode of nickelous acetate solution, in the ortho-acetic acid nickel solution, add some nickelous chlorides and the performance of the electrode that makes has been modified.Best performance by nickelous acetate, nickelous chloride and the prepared electrode of cobaltous acetate solution is listed.Under the situation of using nickel electrode, estimate the performance (seeing Table 2) of electrode by the electrode charge and discharge number of times of measurement before significantly worsening appears in electrode.The electrode charge and discharge cycle is in 7 moles of KOH aqueous solution of 20 ℃, and sweep velocity is to finish under 80 millivolts/second the condition.
Figure 881060909_IMG3
Embodiment 3
Cobalt, iron, nickel and cadmium electrode are pressed embodiment 1 described method preparation.The benchmark that provides one to compare with technology of the present invention is provided, except there not being gas to pass through the electrolyzer, under all identical situation of other condition, has prepared another set of electrode.By in the other method of the present invention, by embodiment 1(a) condition prepare cobalt electrode, but replace oxygen with air.Each anode peak current value is all at 7 moles, and in 25 ℃ the KOH aqueous solution, sweep velocity is to record under 10 millivolts/second the condition.Measured result is listed in table 3.Can find out significantly that by table 3 it is measured to press anode peak current, exist the performance of the electrode of time preparation to be better than the performance of electrode prepared when shortage blasts gas widely blasting oxygen.Under the situation that prepared cobalt electrode when blasting air is arranged, the performance of prepared cobalt electrode was good when this performance blasted gas than nothing, but less than the performance of cobalt electrode prepared when blasting oxygen.
Table 3
Metal The anode peak current of electrode (milliampere/centimetre 2）
No gas is prepared Blast oxygen Blast air
Co Fe Ni Cd 120 105 100 200 505 195 310 650 150 - - -
Embodiment 4
(a) press embodiment 1(a) described method, but each electrode adopts different deposition current to prepare some cobalt electrodes.Result by the table 4a under being summarized in as seen, the optimal deposition current value is 40 milliamperes/centimetre 2This anode peak current (Iap), records with 10 millivolts/second sweep velocitys in 25 ℃ the KOH aqueous solution at 7 moles.
(b) except the deposition current difference, other condition is all by embodiment 1(b) some ferroelectric utmost points of preparation under the fixed condition.The gained result is summarized among the table 4b.Anode peak current (Iap) value is at 7 moles, in 25 ℃ the KOH aqueous solution, with 10 millivolts/second scan speed measurements.
Table 4a
Deposition current (milliampere/centimetre 2) 10 20 40 80 200
The peak point current 375 520 620 510 70 of electrode
(milliampere/centimetre 2)
Table 4b
Deposition current (milliampere/centimetre 2) 40 60 80 100
The peak point current 280 90 310 310 of electrode
(milliampere/centimetre 2)
(c) with being similar to top embodiment 4(a) and (b) described experimental technique, find for Ni, in 1%(weight) NiCl 2Best electroplating current in the aqueous solution is 10 milliamperes/centimetre 2
Embodiment 5
Press embodiment 1(b) described method, but each working electrode adopts different velocities of rotation and prepares some porous iron electrodes.At 7 moles, in 25 ℃ the KOH aqueous solution, measure the anode peak current of each electrode with 10 millivolts/second sweep velocity.Gained the results are shown in table 5.
Table 5
Velocity of rotation (rev/min) 0 200 300 400 600 900 1200
Anode peak current 195 220 270 223 198 210 219
(milliampere/centimetre 2)
Embodiment 6
Be 2.5%(weight with the concentration range) to 15%(weight) different concns electrolytic solution (FeCl 2The aqueous solution) some ferroelectric utmost points of preparation in.Other condition is pressed embodiment 1(b) defined.The anode peak current of finding prepared electrode raises with the concentration of deposited electrolyte to be increased: from 2.5%(weight) time 148 milliamperes/centimetre 2Rise to 15%(weight) 235 milliamperes/centimetre 2
(b) some cadmium electrodes are 1.5%(weight in concentration range) to 10%(weight) the electrolytic solution (CdCl of different concns 2The aqueous solution) preparation in.Other conditions such as embodiment 1(d) middle defined.The anode peak current of prepared electrode reduces with the reduction of the concentration of deposited electrolyte.
(c) some nickel electrodes are 0.7%(weight in concentration range)-5%(weight) the electrolytic solution (NiCl of different concns 2The aqueous solution) preparation in.To the anode peak current with electrode is that the performance of sign is estimated, and the result of gained is summarized among the table 6a.Best performance is from 1%(weight) solution obtain in the electrode for preparing.At different current densities and oxygen gas flow rate, and other condition and embodiment 1(c) influence of the situation deposit metal pair performance of nickel electrodes that the condition of defined is identical is illustrated by the result who is summarized in table 6b.
Figure 881060909_IMG5
Embodiment 7
(add 7 gram Fecl in 100 ml distilled waters at solution of ferrous chloride 2) middle some ferroelectric utmost points of preparation.Condition such as embodiment 1(b) middle defined, but used the difference of listing in the various additives in the table 7 to change.The concentration of additive also is changed.The anode peak current of the electrode that makes like this has been shown in the table 7.The peak inrush current of gained when given data are to use each additive in the table 7, and and the corresponding additive concentration value of this peak inrush current.
At the nickelous chloride (NiCl that exists and do not exist as additive 2) time the prepared ferroelectric utmost point performance in Fig. 5, contrast, it shows at 7 moles, in 40 ℃ the KOH aqueous solution with the excellent peace curve of the measured electrode of 10 millivolts/second sweep velocity.
Embodiment 8
As shown in table 8, in preparation during cadmium electrode, the anode peak current (Iap) of the electrode of gained there are injurious effects by adding acidity that HCl improves electroplate liquid.
Table 7
Additive Optimum amount (milligram) The anode peak current milliampere/centimetre
Bi 2O 3CdCl 2KCl LiOH MnCl 2NiCl 2PbNO 3ZnCl 2N 2H 4·2HCl NiCl 2+N 2H 22HCl is additive-free 14 10 70 50 mg/ml, 7 210 552 210+2.5- 174 104 142 146 152 182 120 154 184 186 140
Embodiment 9
In the electrolyzer of type shown in Figure 2, adopt a nickel foil to replace platinum foil to prepare a ferroelectric utmost point as opposite electrode.The plating bath volume is 100 milliliters, plating bath composed as follows:
3%(weight) NiCl 2
0.03%(weight) N 2H 42HCl
10%(weight) FeCl 2
Used depositing current density is 100 milliamperes/centimetre 24(sees Fig. 2 by the agglomerating plug) oxygen is blasted in this solution.
Because Ni has very high chlorine deposition potential, thus the generation of no chlorine, and oxygen is product unique in this anodic reaction.Compare with the method for embodiment 1, the pH value is remained on a metastable level, thereby might obtain bigger iron deposition.The pure current efficiency of electrode is higher than 80%.Fig. 6 shows nickeliferous, and deposition is 375 milligrams/centimetre 2The volt-ampere curve of the ferroelectric utmost point (in 7 moles KOH, 10 -3The Na of mole 2Among the S, 40 ℃ of temperature, sweep velocity are to record under 10 millivolts/second the condition), and demonstrate this electrode and in the time of 40 ℃, send very high electric current, 0.8 volt the time, electric current is 700 milliamperes/centimetre as the electropotential of relative Hg/Hgo reference electrode 2
Embodiment 10
Fig. 7 shows the contrast of anode performance, and this performance illustrates with the current density of cobalt electrode, and there is time preparation according to the present invention in this electrode blasting oxygen, and another electrode prepares when nothing blasts oxygen.(by the performance estimated at 7 moles, in 25 ℃ the KOH aqueous solution, with 10 millivolts/second scan speed measurements; This cobalt deposition is 60 milligrams).
Fig. 8 shows the similar contrast of the bigger cobalt electrode of a kind of deposition, first electrode (153 milligrams/centimetre of depositions 2) by the present invention's preparation, second electrode is by sintering preparation (deposition: 486 milligrams/centimetre 2).(by the performance estimated at 7 moles, in 25 ℃ the KOH aqueous solution, with 2.5 millivolts/second scan speed measurements).Although sintered electrode has higher deposition, electrode of the present invention moves better.
Embodiment 11
Make cobalt electrode prepared in accordance with the present invention carry out the constant voltage circulation.Anode peak current (Iap) improves with the increase of charge and discharge cycle number of times as shown in Figure 9, and this explanation recirculation helps to improve electrode performance.This anode peak current is at 7 moles, in 25 ℃ the KOH aqueous solution, with 80 millivolts/centimetre 2Sweep velocity record.In iron and nickel electrode, also observed similar results.
Embodiment 12
To what prepare by the present invention, the cobalt deposition is 249 milligrams/centimetre 2Cobalt electrode charge, then with 100 milliamperes/centimetre 2Discharging current discharge.What Figure 10 showed stable state discharges and recharges volt-ampere curve (at 7 moles, recording in 25 ℃ the KOH aqueous solution), illustrates that total pure electrical efficiency of electrode is high under the condition of defined
Embodiment 13
From nickelous acetate, nickelous chloride and cobaltous acetate solution, prepare a kind of nickel electrode (seeing Table method 2 in 2) according to the present invention.This cathodic polarization curve is shown in Figure 11 and (at 7 moles, in 20 ℃ the KOH aqueous solution, records with 10 millivolts/second sweep velocitys; The electrodeposition amount is 73 milligrams/centimetre 2).Because nickel electrode mainly is that people notice that enjoyably electrode according to the present invention is highly active from Figure 11, are 400 milliamperes/centimetre up to current density as negative electrode in battery applications 2The time, polarization is seldom just arranged.After this, (descend～0.2V), and be accompanied by very little polarization, electrode continues to provide another 400 milliamperes/centimetre a very steep pressure drop in operating voltage 2Electric current, this shows and has two negative electrode steps.The step in back may comprise Ni(OH) 2Be reduced into Ni, and perhaps first step is that NiOOH is reduced into Ni(OH) 2In the nickel electrode of routine, because one size of particles and low electroconductibility and never observe this two stage reduction process.This fact may have actual benefit to the rechargeable cell that uses nickel cathode, because it can provide a kind of means easily that charging finishes that detect.
Embodiment 14
Be shown among Figure 12 (in 7 moles, in 25 ℃ the KOH aqueous solution with 10 millivolts/second scan speed measurement) by the anodic polarization curves of the porous cadmium electrode of the present invention preparation.Figure 12 shows that cadmium anodic anode performance has been subjected to very low polarization, and this has represented high reactive behavior and good electrical conductivity
Embodiment 15
KOH/10 at 7 moles -3The Na of mole 2In the S aqueous solution, with 100 milliamperes/centimetre 2Discharging current, be 375 milligrams/centimetre with the monitoring of 25～50 ℃ discharge temps by the iron deposition of the present invention's preparation 2The variation as the anode voltage of the function of time of the ferroelectric utmost point.The results are shown in Figure 13, it has shown a very high utilization ratio.Figure 14 shows the performance that the electrodeposition amount almost decuples a kind of sintered iron electrode of Figure 13 electrode, and this performance is by making this aqueous electrode with 25 milliamperes/centimetre 2Current discharge measured in 30%KOH and 5%LiOH solution.Although it is lower that the sintered electrode of this high deposition demonstrates lower utilization ratio ， And and discharge current density, find that its polarization substantially exceeds by electrode of the present invention.
Embodiment 16
Measure being obtained from according to the current density of the cobalt electrode of various depositions of the present invention.Figure 15 has provided the result of gained, for relatively, together shows the bonding tetrafluoroethylene and the unbonded polytetrafluoroethylstephanoporate stephanoporate NiCo that prepare by thermolysis Ni-Co nitrate 2O 4The measuring result of electrode.(this current density is at 5 moles, in 25 ℃ the KOH aqueous solution, with 1720 millivolts with respect to the efficient hydrogen electrode of DHE() potential measurement).Do not do the ohmic loss compensation for the test result of this cobalt electrode, and to two kinds of NiCo 2O 4The test result of electrode has been done the ohmic loss compensation.Figure 16 represents, under the situation of not carrying out ohm compensation, is the cobalt electrode of 7.5 milli Grams Per Seconds according to deposition of the present invention, current density be 1.1 peaces/centimetre 2In time, seems and is better than this adherent tetrafluoroethylene NiCo widely 4O 4Electrode.

Claims (37)

1, a kind of technology that on a support material, produces a kind of electrodepositable metal porous layer, it comprises: this support material is immersed in the electrolytic medium that contains this metal ion species, then under the situation of a kind of oxidizing substance near the electrolytic medium the support material of being provided in is arranged, on this support material, this oxidizing substance and this metal reaction form a kind of product that can be reduced under mode of deposition with this metal electrodeposition.
2, a kind of technology according to claim 1 wherein, provides continuously when this metal of deposition, or produces this oxidizing substance.
3, a kind of technology according to claim 1 or 2, wherein this oxidizing substance is a kind of oxygen containing oxidizing substance.
4, a kind of technology according to claim 3, wherein oxygen containing oxidizing substance is an oxygen, or a kind of oxidizing substance that results from oxygen under mode of deposition.
5, a kind of technology according to claim 4, wherein this oxygen containing oxidizing substance is, or results from and be introduced into electrolytic medium, to make it to pass near the gaseous oxygen the support material.
6, a kind of according to technology one of any in the claim 1 to 5, the another kind of oxidizing substance near this medium the support material of being provided in is wherein arranged, it and this metal reaction form a kind of under mode of deposition reducible product.
7, a kind of technology according to claim 6, wherein this another kind of oxidizing substance is to be selected from halide ions, halogen and the negatively charged ion that can be formed by halogen and halide ions under mode of deposition.
8, a kind of technology that on support material, produces the porous layer of electrodepositable metal, it comprise this support material immersed the ionic electrolytic medium Zhong ， And that contains this metal and when the gaseous oxygen that is imported into this electrolytic medium in the mode of passing near this support material surface is arranged with this metal electrodeposition on support material.
9, a kind of technology according to Claim 8, wherein this electrolytic medium contains a kind of halide ions.
10, according to Claim 8 a kind of or 9 technology, wherein this electrolytic medium contains a kind of halogen.
11, a kind of one of any technology in 10 according to Claim 8, wherein this electrolytic medium contains oxyhalide ion.
12, a kind of according to one of any technology in the claim 1 to 11, wherein contain the ion of two or more metals in this electrolytic medium, so contain two kinds of metals in the porous layer of making so at least.
It is 13, a kind of that wherein this electrolytic medium contains two or more metal ions according to one of any technology in the claim 1 to 11, wherein a kind of and oxidizing substance reaction form a kind of under mode of deposition unreducible product.
14, a kind of according to one of any technology in the claim 1 to 13, wherein, support material is rotated when metal deposition.
15, a kind of technology according to any claim in the claim 1 to 14, wherein, the composition of this electrolytic medium changes by add one or more materials in this electrolytic medium in deposition process, so the metal porous layer of making like this has the layer in several layers of different particle structures zone.
16, a kind of according to technology one of any in the claim 1 to 15, wherein this porous layer comprises a kind of metal that is selected from transition metal.
17, a kind of technology according to claim 16, wherein this transition metal is selected from cobalt, iron, nickel and cadmium.
18, a kind of according to technology one of any in the claim 1 to 17, wherein this electrolytic medium is a kind of aqueous electrolytic medium.
19, a kind of technology according to claim 18, wherein this metal is that a kind of transition metal ， And and deposition current are not more than 300 milliamperes/centimetre 2
20, a kind of technology according to claim 19, wherein this deposition current is not more than 100 milliamperes/centimetre 2
21, a kind of wherein this ionogen is a kind of fused salt according to one of any technology in the claim 1 to 15, and this metal is a kind of refractory metal.
22, a kind of wherein this electrolytic medium is a kind of organic electrolysis medium according to technology one of any in the claim 1 to 15, and this metal is a kind of basic metal.
23, a kind of technology that on support material, generates a kind of porous metal oxide, it comprises by generate the porous layer of this metal on support material according to technology one of any in the claim 1 to 22, and then after this porous metallic layers generates, make this porous layer anodic oxidation and form a kind of oxide compound of this metal.
24, a kind of technology according to claim 23, wherein this porous layer contains two or more metals, and in order to make first metal all oxidized basically when the anodic oxidation, and whole second metal keeps elementary state basically, and these metals are selected.
25, a kind of technology according to claim 23, wherein this porous layer contains two or more metals, and these metals are oxidized and generate the blended oxide compound when anodic oxidation.
26, a kind of technology according to right 25, wherein these metals are selected like this, so that these metals are converted into a kind of stupalith when anodic oxidation.
27, a kind of according to technology one of any in the claim 23 to 26, wherein this support material is made of copper.
28, a kind of technology that on tubing, forms a successive ceramic coat, it comprises passes this tubing in one electrolytic medium, on tubing, generates a metal porous layer by using therein, then this tubing insertion is made in the anodized zone of this porous metallic layers with shape one ceramic layer according to technology one of any in the claim 1 to 22.
29, a kind of technology that makes electrode regeneration in electrolyzer, it comprises by forming the layer of metal porous layer according to technology one of any in the claim 1 to 22 on electrode.
30, a kind of technology for preparing a kind of electrode, it comprises: use according to method one of any in the claim 1 to 22 to prepare the layer of metal porous layer to form an electrode on support material, make this electrode stand the constant voltage circulation then.
31, a kind of technology of a kind of metal porous layer of preparation described in one of any as this paper embodiment 1 to 9 basically.
32, a kind of all porous metal of in using, being produced during one of any technology according to claim 1 to 22 or 33.
33, a kind ofly allly using the goods of making according to one of any technology in the claim 1 to 31.
34, a kind of goods with average particle size particle size less than the porous metal part of 3 μ.
35, a kind of goods according to right 34, it is included in the thin and thick particle in the size range of 0.05 μ to 1 μ.
36, a kind of according to one of any goods in the claim 33 to 35, wherein these goods are a kind of electrode pads, a kind of strainer, a kind of support of the catalyst or a kind of catalysis electrode.
37, a kind of battery of using according to the made electrode of technology one of any in claim 1 to 25 or 28 to 31 that comprises.
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GB9007105D0 (en) * 1990-03-29 1990-05-30 Dowty Electronic Components A battery
GB9405518D0 (en) * 1994-03-21 1994-05-04 Mupor Ltd Porous metal composite body
US6596187B2 (en) * 2001-08-29 2003-07-22 Motorola, Inc. Method of forming a nano-supported sponge catalyst on a substrate for nanotube growth
CN103367756B (en) * 2013-07-22 2015-06-10 山东大学 Preparation method of porous copper based lithium ion battery anode material
US10991948B1 (en) * 2020-03-20 2021-04-27 Chang Chun Petrochemical Co., Ltd. Surface-treated copper foil for lithium-ion secondary batteries

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FR2481717A1 (en) * 1980-05-05 1981-11-06 Anvar Electrochemical prepn. method for solar surface - comprising forming grey nickel deposit and anodising
DE3307303A1 (en) * 1983-03-02 1984-09-06 Matthias 8757 Karlstein Faber Electrochemical process for producing active masses for the nickel or cadmium electrode, preferably in a nickel/cadmium storage battery
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CN103422116B (en) * 2013-08-15 2016-08-17 重庆大学 A kind of porous Ni-base ru oxide is combined the preparation method of hydrogen-precipitating electrode
CN106884190A (en) * 2015-12-15 2017-06-23 中国科学院大连化学物理研究所 A kind of preparation of classifying porous material and classifying porous material

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